Fuel additive



United States Patent 3,332,755 FUEL ADDITIV E Ira Kukin, West Orange, N.J., assignor to Apollo Chemical Corp., Clifton, N.J., a corporation of New York No Drawing. Filed June 3, 1964, Ser. No. 372,380 26 Claims. (Cl. 444) The present invention relates to substances adapted to be added to fuels in order to improve the combustion characteristics of the fuel and reduce the adverse effects of combustion products on the structures with which they come in contact. The invention is particularly, although not exclusively, advantageous in connection with the use of fuel for motive power purposes, where the combustion products of the fuel are used either to produce steam or to act directly on turbine wheels.

Fuels are usually burned in enclosures lined with refractory material and the products of combustion make contact with that refractory lining. The products of combustion then pass from the furnace to a utilization area. Sometimes this utilization area comprises the tubes of a steam generating system, the products of combustion passing around those tubes and transferring the heat which they carry to the water in the tubes, changing that Water to steam or superheating already-formed steam. In other instances the utilization chamber comprises a turbine, which the products of combustion directly im pinging against the blades of the turbine. Wherever the products of combustion engage a structural element an interaction-between them can take place, depending upon their respective natures. Often this interaction has deleterious effects, and the extent of those effects depends to an appreciable extent upon the chemical content of the original fuel and the temperature of the combustion products. Even traces of such elements as vanadium, sodium and sulphur in the fuel produce troublesome, and often exceedingly disadvantageous, effects on the structures with which the combustion products come into contact.

In some instances the combustion products react with the refractory bricks in the furnace or with the cement which holds those bricks together in order to deteriorate either the bricks, cement or both, thus hastening the day when the furnace must be closed down and relined, an exceedingly expensive operation. Contact between the combustion products and the fireside boiler tubes, as well as the economizers, preheaters and stacks of boilers, produces corrosion of those metal structures, hastening the day when the furnace must be shut down so repair or replacement of these structural elements can be carried out. The corrosion is intensified when the combustion products form deposits, usually sticky and tenacious in nature, on these structural elements. The combustion products will also tend to form ash deposits which not only have a corrosive effect, but also tend to accumulate and block the passages through which the hot gases are designed to pass.

The problems produced by these combustion products are generally well recognized. It is believed that various chemical reactions are involved. Thus the formation of low melting point deposits on the furnace walls and furnace supports are believed to act as fluxing agents and mineralizers on hot refractory material, leaching out the refractory components and dissolving the adhesive between the refractory bricks. Moreover, it is believed that these low melting slags cause low temperature condensation of corrosive sulphuric acid to take place, thus intensifying the breakdown of the refractory material. The corrosion of such structural elements as fireside tubes, economizers, stacks and the like result from comparable causes.

The problems involved are particularly acute in con nection with gas turbines operating with residual fuels, where the gaseous vapors laden with sodium-, vanadiumand/or sulphur-containing ashes form deposits on the turbine blades which not only corrode those blades but also impede proper turbine action. The problems involved are also particularly acute in steam boilers of marine vessels where, because of space limitations, the superheater tubes are spaced quite close to one another with only narrow passageways between them. Ash which builds up on the superheater tubes will cause blockage of those narrow passageways, necessitating -a costly and laborious cleaning-out period, and the greater the density and tenacity of that ash, the more difficult is the cleaning operation. In any boiler the build-up of ash on the tubes, in addition to impede the flow of hot gas between the tubes, also acts adversely upon the transfer of heat through the tubes, thus reducing the efficiency of the boiler.

One approach which has been taken to this problem in the past has been to add substances to the fuel which would react or coact with the troublesome combustion products in order to minimize their adverse effects. Thus, it has been proposed that there be injected into the fuel or firing zone comparatively massive dosages of materials such as the oxides, hydroxides, carbonates and other salts of magnesium, calcium, aluminum, zinc, sodium, silicon, manganese and various of the rare earth metals. The addition of clays such as dolomite, talc and magnesias has also been suggested. These procedures, however, have not proved satisfactory, largely because the dosages of beneficial metal which must be added if any appreciable desirable effects are to occur have been excessive. For example, the addition of magnesium, as previously suggested, involves the use of 3 mols of magnesium for each mol of vanadium in the fuel. Such relatively massive dosages of additive have not only involved excessive cost insofar as the materials themselves are concerned, but various secondary adverse effects exist-the large amounts of additive themselves produce appreciable quantities of dense, tenacious ash which tend to block the passages between the tubes; when the additive is added to a fuel oil, the fuel oil pumps exhibit excessive wear; the handling of such large amounts of additive involves an excessive amount of care and attention on the part of maintenance and operation personnel. Moreover, in many instances the results promised by the proponents of such additives did not materialize, or else did not reliably materialize in all instances.

The prime object of the present invention is to devise an additive for use With fuels which will reliably overcome the adverse effects of vanadium, sulphur and sodium contents of fuels at least to a substantial degree, and which Will involve the use of considerably smaller amounts of additive materials than have heretofore been thought possible.

The invention is applicable for use with all fuels having vanadium, sulphur and/or sodium content. Residual petroleum fuels are typical, as are coal and coke. The precise manner in which the additive is provided is not critical. It may be combined with the fuel before combustion (mixed with a liquid fuel or coated, either in liquid or powdered form, onto a solid fuel), it may be Patented July 25, 1967 3 injected into the furnace concurrently with the fuel, or it may be injected separately into the furnace just be yond the fire zone.

I have discovered that when the additive is composed or coacts with the deleterious combustion products in such a way as to result in the production of an ash which is porous, light and non-tenacious, and which therefore produces much less corrosion, and much less built-up and passage-blocking accumulations, than has previously been thought possible.

The additive of my invention comprises a first constituent which contains aluminum, magnesium or manganese, a second constituent which contains one of the elements of that group other than the first constituent, and a third constituent containing iron. The first constituent is present in the additive in major proportions compared with the second and third constituents, but in appreciably lesser proportions than has heretofore been taught as a fuel additive. The second and third constituents are present in the additive in comparatively minor proportions. Thus when the first constituent contains aluminum, the second constituent may contain manganese. When the first constituent contains magnesium, the second constituent may contain manganese. When the first constituent contains manganese, the second constituent may contain aluminum. The third constituent in each case contains iron. In a typical example the first constituent is present in the additive in an amount such that the proportions by weight of its active element (aluminum, magnesium or manganese) is between 5 and 30% of the Weight of the entire additive, Whereas the second and third constituents are present in active element proportions by weight between 0.35 and of the additive. In a typical use of such an additive with a fuel having a given vanadium content, the additive is used in such proportions with the fuel, and the constituents are present in the additive in such proportions, that the weight ratios of the active element of the first constituent to the vanadium content of the fuel is as 1:2, the second and third constituents being present in weight ratios of 1:14-40.

In order to indicate the substantial difference between the amounts of additive required in accordance with the present invention and those called for in the prior art, the following comparison is presented: Prior art suggestions for the use of aluminum oxide called for the use of at least 2 mols of aluminum for each mol of vanadium in the fuel, with the use of 3 mols of aluminum per mol of vanadium being preferred; In accordance with my invention, when aluminum constitutes the first constituent of my additive, a mol ratio of aluminum to vanadium of approximately 1:1 is utilized. Similar comparisons may be made between prior art suggestions for the use of magnesium or manganese compounds, and the additives of the present invention where magnesium or manganese compounds comprise the. first consituent of the additive.

The reasons for the surprising beneficial results obtained through the use of such small amounts of additive are not known with certainty, and the instant invention may therefore be considered as empirical in nature. It may be that there is a catalytic or synergistic effect involved. I believe that the addition of the very small amount of the second and third'constituents so alters the way in which the first constituent reacts with the deposit-forming components of the fuel as to produce the porous, light and non-tenacious ash which is characteristic of the use of my invention. That ash is much more easily removed from furnace and boiler walls through routine cleaning steps (soot blowers or simple air lancing) .4 than are the ashes produced in accordance with prior art teachings. Moreover, the ash produced in accordance with the present invention appears to be far less reactive, and to have a far smaller corrosive effect on the refractory materials, cements and metal surfaces of furnaces, boilers and turbines, than has heretofore been the case.

The active elements used in the additive of the present invention are normally provided in the form of oxides, hydroxides, or carbonates of the active elements involved. The aluminum-containing compounds are preferably in the form of specially precipitated alumina, alumina hydrate (often in the form of by-product slurries), finely calcined aluminum oxides, and aluminum-containing clays such as bauxite. The particle size of the aluminum-containing active component is preferably between 0.1 and 15 microns, with a particle size range between 0.5 and 3 microns giving superior results. Optimum particle size appears to increase the porosity of the ash which is formed. The magnesium-containing constituent is preferably in the form of finely pulverized or finely precipitated magnesium oxide from sea water extraction, calcined magnesium oxides and hydroxides, preferably from naturally occurring magnesia ores or derived from sea water, magnesium carbonate or basic magnesium carbonate. The manganese-containing compounds are preferably in the form of naturally occurring or derived manganese dioxides or manganese-containing clays, as well as manganese dioxides by-product slurries derived from refining. The particle size of the manganese-containing substances is preferably between 0.1 and 15 microns.

The iron-containing compounds are preferably in the form of natural or artificial ferric, ferrous, or ferrousferric oxides or ferrous carbonate, but it can also be in the form of an oil-soluble iron tallate, naphthenate, sulfonate, or carbonyl, or even metallic iron, preferably present in particle sizes between 0.1 and 10 microns.

A typical additive will comprise the above constituents mixed with a liquid in which those constituents are dissolved or dispersed, and to which mixture other substances may be added, as is known in the field, for various known purposes. Typically the additive will comprise a diluting oil or solvent together with a surfactant, a glycol, a gelling agent, a hydrophilic colloid and water.

The following Examples 1-3 describe the compounding of typical additive mixtures in accordance with the present invention, Example 1 utilizing an aluminum-containing substance as the first constituent and a manganese-containing substance as the second constituent, Example 2 utilizing a magnesium-containing substance as the first constituent and a manganese-containing substance as the second constituent, and Example 3 utilizing a manganesecontaining substance as the first constituent and an aluminum-containing substance as the second constituent.

Example 1 To a high-shear mixer such as a Hockmeyer, Cowles Dispersator, Banbury, Morehouse, or Premier Colloid mill, or to an attritor such as a batch size or continuous ball mill, a sand mill or a pebble mill, or to a three-roll Mix for a period of V2 to 3 hours, and then add to the charge as follows:

' Parts by weight Hydrophilic colloid Water 8.5

The resultant product will be liquid and fluid at room temperatures with less than 1% settling after six months.

Example 2 Follow procedure of Example 1use following charge: Parts by weight Surfactant 4.5 Diluting oil or solvent 18.0 Ethylene glycol monomethyl ether 7.5 Gelling agent or pigment stabilizer 0.3 Magnesium hydroxide 38.0 Iron oxide 1.0 Manganese dioxide 1.5

followed by:

Parts by weight The specific parts by weight set forth in Examples 1-3 are but typical. The surfactant can be provided in a range between 2 and 25 parts, the diluting oil or solvent in a range between and 40 parts, the glycol in a range between 2 and parts, the gelling agent or pigment stabilizer in a range between 0.1 and 3 parts, the hydrophilic colloid in a range between 0.2 and 4.0 parts and the water in a range between 6 and 30 parts.

The surfactant may be any substances known to have such properties. Particularly effective are the ammonium, amine, hydroxyl amine, quaternary amine, calcium, magnesium, zinc or barium salts of (a) tall oil fatty acid, naphthenic acids, octoic or ethylhexoic acids, long chain or oil-soluble carboxylic (fatty) acids of natural or synthetic origin; (b) sulfonic acids of petroleum or synthetic origin; (c) oil-soluble alkyl phenols, as well as organic phosporous compounds, phosphorous-sulphide treated olefins, non-ionic oil soluble surfactants and cationic oilsoluble surfactants, many of which are disclosed in British Patent 846,174 of Aug. 24, 1960.

Typical diluting oils or solvents are volatile petroleum distillates, pale oils preferably of naphthenic origin, cresylic acid solvents from coal tar distillations, and liquid amines.

Typical glycols which may be used are ethylene glycol, propylene glycol, hexylene glycols, etc., glycerol, glycol ethers and glycol esters (Cellosolves and Carbitols).

Typical gelling agents which may be used are various organophilic bentonites, aluminum stearate, zinc stearate, and various polymethacrylate derivatives.

Typical hydrophilic colloids which may be used are magnesium aluminum silicates, hydrophilic bentonites, synthetic resins having a high water-absorptive capacity, starches and modified starches and gums, carboxymethyl celluloses, and Carbopols (B. F. Goodrich Co.).

In lieu of water, glycols can be substituted completely, but a highly polar water phase is preferred in order to swell the pigments so that they will remain suspended in the vehicle without coalescing.

The precise form in which the additive is provided is not critical. Thus it may be provided as a dispersion of the active constituents in an oil phase, as an aqueous emulsion of those constituents, or as a dry mixture.

Set forth 'below in Table I are the range of proportions by weight of the active constituents of the additives for Examples 1, 2 and 3 above, Example 1 having an aluminum-containing substance as its first or major constituent and having a manganese-containing substance as its second constituent, Example 2 having a magnesiumcontaining substance as its first constituent and a manganese-containing substance as its second constituent, and Example 3 having a manganese-containing substance as its first constituent and an aluminum-containing substance as a second constituent. That table also shows the proportions by weight of typical actual compounds which may be used to provide the active elements in question. Table II is similar except that it shows a preferred range of the constituents in question.

TABLE I-GENERAL RANGE Ex. 1 Ex. 2 Ex. 3

Percent .Al 5-25 0. 5-5. 0 Percent M2 10-30 Percent Mn 0. 5-5. 0 0. 5-5. 0 5-25 Percent Fe 0. 35-3 5 0. 35-3. 5 0. 35-10 Above provided by- Percent Hydrated alumina 1 15-75 1. 5-13 Percent Mg(0H) 2 25-75 Percent MnO; 0.8-9. 0 9-40 Percent F8103 0. 5-5 0. 5-16 1 The use of 75% hydrated alumina to supply 25% aluminum metal would be somewhat high in order to produce a fluid end product. For this case, calcined alumina or amixture of hydrated alumina and calcined alumina would be preferable in order to leave room for solvent to liquify the product.

2 Here again 75% of magnesium hydroxide would not leave room for solvent and calcined magnesium oxide would be required.

TABLE II.P REFERRED RAN GE If desired the additives of the present invention may also contain additional substances which produce additional known beneficial results. Indeed, when such known substances are included in the additive of the present invention, it :has been discovered that they may be used in much lesser proportions than has heretofore been thought necessary in order to produce their desired specific results.

Thus zirconium or zircons may be added to increase the melting points of the oil-ash complexes or to alter the structural patterns of the oil-ash complexes. 15% of zirconium silicate or zirconium oxide are highly effective in this regard, and even at the highest percentages in a typical installation only one part of zirconium would be provided for 8 parts of vanadium in the fuel. This compares most favorably with the zirconiumzvanadium ratio of 1:35 which has previously been suggested.

Talc may be added to stabilize the oil or aqueous dispersion of the additive combination. Only 15% of talc need thus be added when it is desired.

Additional small amounts (1-5%) of magnesium-containing compounds in the forms of oxides, hydroxides, carbonates or naphthenates may be added to the additives of the type of Examples 1 and 3 in order to assist in the neutralization of sulphur trioxide in the low temperature sections of the boilers.

From 1 to 10% of antimony oxide, or certain known arsenic or chlorine compounds, may be added to produce their known poisoning effect on the catalytic activity of a similar purposes.

In all these instances the amounts of such additives are far below that previously taught as necessary in order to produce beneficial eifects, whether used alone or in combination with other prior art additives.

The amount of additive to be combined with the fuel will depend upon many factors, such as the operating temperature of the superheated steam, the design of the boiler, the burner configuration, and, of course, the impurity content of the fuel. The higher the operating temperature of the superheated steam the greater is the tendency toward the formation of slag and the corrosion of the tube supports or hangers. With narrowly spaced superheated tubes the tendency to clog the passage between the tubes is greater. The configuration of certain boilers, and particularly marine boilers, is such, primarily because of compact design, that good fi-ame patterns do not occur and as a result there is a heavy ash accumulation and rapid deterioration of the brickwork. The greater the vanadium, sodium and/ or sulphur content of the fuel, the greater is the tendency toward the production of deleterious combustion products. The amount of additive to be combined with the fuel will, of course, be greater as any of these disadvantageous situations increases in intensity.

In a typical installation one gallon of additive (weighing -11 lbs.) and consisting of approximately 50% active solids, is added to 4000 gallons of residual petroleum fuel. To put the matter another way, a typical residual fuel may have a vanadium content of 100 parts per million, a sodium content of 25 parts per million and a sulphur content of 2 parts per hundred. With such a fuel, additive is combined in proportions of 0.035% by weight of additive to fuel.

With these proportions, there is set forth below in Table III the percentages by weight of active element constituents of the additives of Examples 1, 2 and 3 above as its active elements are present in the fuel-additive combination.

TABLE III Percent AL... Percent Mg. Percent Mn Percent Fe- Set forth below in Table IV are the weight ratios of active element constituents to the vanadium content of the fuel after the additive has been combined therewith.

TABLE IV Ex. 1' Ex. 2

sirable for use where combustion problems, and 'particularly the minimization of the formation of sulphur trioxide, are of significance. The presence of the second and third constituents greatly enhances the known action of the manganese-containing compounds as a slag modifier, oil-ash corrosion inhibitor, and particularly as a low temperature inhibitor for the conversion of sulphur dioxide to sulphur trioxide, and with the presence of the manganese in appreciable amounts, higher amounts of iron-containing compounds appear to be called for.

Additives of the type of Example 1, in which an aluminum-containing compound constitutes the first additive constituent, appear to give best results Where ash production is the major problem. Additives of the type of Example 2, in which a magnesium-containing compound constitutes the first constituent, appear to be preferable where corrosion is the major factor and where turbines are involved. Additives of the type of Example 3, where manganese-containing compounds constitute the first constituent, are desirable where more efiicient fuel burning is the major desideratum.

Through the use of the combinative additive of the present invention, one is enabled to use appreciably smaller amounts of additive compounds than has previously been the case, and such compounds may be employed even when the sodium chloride content of the fuel is relatively high, a factor which normally is considered as adversely afiecting the action of additives. It is further noteworthy that iron compounds, usually considered undesirable because of their tendency to form low melting point slags, are very decidedly advantageous in connection with the present invention.

Despite the fact that smaller amounts of additive material than is customary are employed in'accordance with the present invention, the beneficial results achieved thereby are superior to, and more dependably attained, than those which attend prior art additives. Thus better and more reliable results are achieved in accordance with the present invention, at a lesser cost and without the secondary effects which have militated against prior art suggestions along these lines.

While but a limited number of embodiments of the present invention are here specifically disclosed, it will be apparent that many variations may be made therein, all within the scope of the invention as defined in the following claims.

I claim:

1. A fuel composition having improved slag-forming characteristics comprising a major amount of a fuel from.

a class consisting of residual petroleum fuel, coal and coke, fuel containing a member from the class consisting of vanadium, sulphur and sodium, and a minor amount of an additive consisting essentially of a first constituent which comprises a member of the first class consisting of aluminum, magnesium and manganese, a second constituent which comprises a member of said first class other than that comprising said first constituent, and a third constituent which comprises iron, said first constituent being present in active element proportions by weight between 5 and 30 parts, said second and third constituents being present in active element proportions by weight between 0.35 and 10 parts, said additive being efifective to minimize the deleterious effects of said vanadium, sulphur and sodium when combustion of said fuel occurs.

2. The composition of claim 1, inwhich said aluminum is in the form of alumina, said magnesium is in the form of oxides, hydroxides or carbonates of magnesium, said manganese is in the form of manganese dioxide or manganese-containing clays, and said iron is in the form ing a size between 0.5 and 3 microns, said iron and its compounds are in the form of particles having a particle size between 0.1 and microns, said manganese and its compounds are in the form of particles having a size between 0.1 and microns, and said magnesium and its compounds are in finely divided form.

5. The composition of claim 1, in which said first and third constituents are in the form of particles having a size between 0.1 and 15 microns.

6. The composition of claim 1, in which said aluminum and its compounds are in the form of particles having a size between 0.5 and 3 microns, said iron and its compounds are in the form of particles having a particle size between 0.1 and 10 microns, said manganese and its compounds are in the form of particles having a size between 0.1 and 15 microns, and said magnesium and its compounds are in finely divided form.

7. A fuel composition having improved slag-forming characteristics comprising a major amount of a fuel from a class consisting of residual petroleum fuel, coal and coke, fuel containing a member from the class consisting of vanadium, sulphur and sodium, and a minor amount of an additive consisting essentially of a first constituent which comprises a member of the first class consisting of aluminum, magnesium and manganese, a second constituent which comprises a member of said first class other than that comprising said first constituent, and a third constituent which comprises iron, said first constituent being present in active element proportions by weight between 9 and parts, said second and third constituents being present in active element proportions by weight between 0.6 and 4 parts, said additive being effective to minimize the deleterious effects of said vanadium, sulphur and sodium when combustion of said fuel occurs.

8. The composition of claim 7, in which said aluminum is in the form of alumina, said magnesium is in the form of oxides, hydroxides or carbonates of magnesium, said manganese is in the form of manganese dioxide or manganese-containing clays, and said iron is in the form of oxides or carbonates of iron.

9. The composition of claim 8, in which said first and third constituents are in the form of particles having a size between 0.1 and 15 microns.

10. The composition of claim 8, in which said aluminum and its compounds are in the form of particles having a size between 0.5 and 3 microns, said iron and its compounds are in the form of particles having a particle size between 0.1 and 10 microns, said manganese and its compounds are in the form of particles having a size between 0.1 and 15 microns, and said magnesium and its compounds are in finely divided form.

11. The composition of claim 7, in which said first and third constituents are in the form of particles having a size between 0.1 and 15 microns.

12. The composition of claim 7, in which said aluminum and its compounds are in the form of particles hav ing a size between 0.5 and 3 microns, said iron and its compounds are in the form of particles having a particle size between 0.1 and 10 microns, said manganese and its compounds are in the form of particles having a size between 0.1 and 15 microns, and said magnesium and its compounds are in finely divided form.

13. A fuel composition having improved slag-forming characteristics comprising a major amount of a fuel from a class consisting of residual petroleum fuel, coal and coke, and a minor amount of an additive consisting essentially of a first constituent which comprises a member of the first class consisting of aluminum, magnesium and manganese, a second constituent which comprises a member of said first class other than that comprising said first constituent, and a third constituent which comprises iron, said fuel having a vanadium content and said additive and fuel being present in proportions such, and said first, second and third constituents being present in said addi tive in proportions such, as to produce in the mixture substantially the following weight ratios of active constituent element to vanadium element: first constituent- 1:2, second and third constituents1:1420, said additive being effective to minimize the deleterious effects of said vanadium when combustion of said fuel occurs.

14. The composition of claim 13, in which said aluminum is in the form of alumina, said magnesium is in the form of oxides, hydroxides or carbonates of magnesium, said manganese is in the form manganese dioxide or manganese-containing clays, and said iron is in the form of oxides or carbonates of iron.

15. The composition of claim 14, in which said first and third constituents are in the form of particles having a size between 0.1 and 15 microns.

16. The composition of claim 13, in which said first and third constituents are in the form of particles having a size between 0.1 and 15 microns.

17. A fuel composition having improved slag-forming characteristics comprising a major amount of a fuel from the class consisting of residual petroleum fuel, coal and coke, fuel containing a member from the class consisting of vanadium, sulphur and sodium, and a minor amount of an additive consisting essentially of a first constituent which is a member of the class consisting of alumina, alumina hydrate, aluminum oxide, and aluminumcQntaining clays, a second constituent which is a member of the class consisting of manganese dioxide and manganese-containing clays, and a third constituent which is a member of the class consisting of oxides and carbonates of iron, said first constituent being present in active element proportions by weight between 9-15 parts, said second constituent being present in active element proportions by weight between 0.9-3 parts, and said third constituent being present in active element proportions by weight between 0.6-2 parts, said additive being effective to minimize the deleterious effects of said vanadium, sulphur and sodium when combustion of said fuel occurs.

18. A fuel composition having improved slag-forming characteristics comprising a major amount of a fuel from the class consisting of residual petroleum fuel, coal and coke, fuel containing a member from the class consisting of vanadium, sulphur and sodium, and a minor amount of an additive consisting essentially of a first constituent which is a member of the class consisting of hydroxides and carbonates of magnesium, a second constituent which is a member of'the class consisting of manganese dioxide and manganese-containing clays, and a third constituent which is a member of the class consisting of oxides and carbonates of iron, said first constituent being present in active element proportions by weight between 15-20 parts, said second constituent being present in active element proportions by weight between 0.9-3 parts, and said third constituent being present in active element proportions by weight between 0.62 parts, said additive being effective to minimize the deleterious elfects of said vanadium, sulphur and sodium when combustion of said fuel occurs.

19. A fuel composition having improved slag-forming characteristics comprising a major amount of a fuel from the class consisting of residual petroleum fuel, coal and coke, fuel containing a member from the class consisting of vanadium, sulphur and sodium, and a minor amount of an additive consisting essentially of a first constituent which is a member of the class consisting of manganese dioxide and manganese-containing clays, a second constituent which is a member of the class consisting of alumina, alumina hydrate, aluminum oxide, and aluminum-containing clays, and a third constituent which is a member of the class consisting of oxides and carbonates of iron, said first constituent being present in active element proportions by weight between 9-15 parts, said second constituent being present in active element proportions by weight between 0.6-3.0 parts, and said third constituent being present in active element proportions by weight between 1-4 parts, said additive being effective 1 1 to minimize the deleterious effects of said vanadium, sulphur and sodium when combustion of said fuel occurs.

20. The method of minimizing the deleterious effects of vanadium, sulphur and sodium in fuel compositions from the class consisting of residual petroleum, coal and coke which comprises burning said fuel in the presence of a minor amount, relative to said fuel, of an additive consisting essentially of a first constituent which comprises a member of the first class consisting of aluminum, magnesium and manganese, a second constituent which comprises a member of said first class other than that comprising said first constituent, and a third constituent which comprises iron,said first constituent being present in active element proportions by weight between 5 and 30 parts, said second and third constituents being present in active element proportions by weight between 0.35 and parts.

21. The method of claim 20, in which said aluminum is in the form of alumina, said magnesium is in the form of oxides, hydroxides or carbonates of magnesium, said manganese is in the form of manganese dioxide or manganese-containing clays, and said iron is in the form of oxides or carbonates of iron.

22. The method of minimizing the deleterious effects of vanadium, sulphur and sodium in fuel compositions from the class consisting of residual petroleum, coal and coke which comprises burning said fuel in the presence of a minor amount, relative to said fuel, of an additive consisting essentially of a first constituent which comprises a member of the first class consisting of aluminum, magnesium and manganese, a second constituent which comprises a member of said first class other than that comprising said first constituent, and a third constituent which comprises iron, said first constituent being present in active element proportions by weight between 9 and parts, said second and third constituents being present in active element proportions by Weight between 0.6 and 4 parts.

23. The method of claim 22, in which said aluminum is in the form of alumina, said magnesium is in the form of oxides, hydroxides or carbonates of magnesium, said manganese is in the form of manganese dioxide or manganese-containing clays, and said iron is in the form of' oxides or carbonates of iron.

24. The method of minimizing the deleterious effects of vanadium, sulphur and sodium in fuel compositions from the class consisting of residual petroleum, coal and coke which comprises burning said fuel in the presence of a minor amount, relative to said fuel, of an additive consisting essentially of a first constituent which is a member of the class consisting of alumina, alumina hydrate, aluminum oxide, and aluminum-containing clays, a second constituent which is a member of the class consisting of manganese dioxide and manganese-containing clays, and a third constituent which is a member of the class consisting of oxides and carbonates of iron, said 12 first constituent being present in active element proportions by weight between 9-15 parts, said second constituent being present in active element proportions by weight between 0.9-3 parts, and said third constituent being present in active element proportions by weight between 0.6-2 parts.

25. The method of minimizing the deleterious effects of vanadium, sulphur and sodium in fuel compositions from the class consisting of residual petroleum, coal and coke which comprises burning said fuel in the presence of a minor amount, relative to said fuel, of an additive consisting essentially of a first constituent which is a member of the class consisting of oxides, hydroxides and carbonates of magnesium, a second constituent which is a member of the class consisting of manganese dioxide and manganesecontaining clays, and a third constituent which is a member of the class consisting of oxides and carbonates of iron, said first constituent being present in active element proportions by weight between 15-20 parts, said second constituent being present in active element proportions by weight between 0.9-3 parts, and said third constituent being present in active element proportions by Weight between 0.6-2 parts.

26. The method of minimizing the deleterious effects of vanadium, sulphur and sodium in fuel compositions from the class consisting of residual petroleum, coal and coke which comprises burning said fuel in the presence of a minor amount, relative to said fuel, of an additive consisting essentially of :a first constituent which is a member of the class consisting of manganese dioxide and manganese-containing clays, a second constituent which is a member of the class consisting of alumina, alumina hydrate, aluminum oxide, and aluminum-containing clays, and a third constituent which is a member of the class consisting of oxides and carbonates of iron, said first constituent being present in active element proportions by weight between 9-15 parts, said second constituent being present in active element proportions by weight between 0.6-3.0 parts, and said third constituent being present in active element proportions by weight between 1-4 parts.

References Cited UNITED STATES PATENTS 846,338 3/ 1907 McNamara 44-4 1,894,682 1/1933 Haas 444 2,890,108 6/1959 Toulrnin 4467 2,943,925 7/ 1960 Ambrose 4468 2,986,456 5/1961 Toulmin 4467 FOREIGN PATENTS 544,038 7/1957 Canada.

490,064 8/ 1938 Great Britain.

306,651 7/ 1955 Switzerland;

DANIEL E. WYMAN, Primary Examiner. C. F. DEBS, Assistant Examiner.

Disclaimer and Dedication 3,332,755.Ira Kukin, West Orange, NJ. FUEL ADDITIVE. Patent dated July 25, 1967. Disclaimer and Dedication filed Mar. 10, 1983, by the assignee, Economics Laboratory, Inc. Hereby enters this disclaimer to all claims and dedicates to the Public the entire term of said patent.

[Official Gazette October 4, 1983.] 

20. THE METHOD OF MINIMIZING TGHE DELETERIOUS EFFECTS OF VANADIUM, SULPHUR AND SODIUM IN FUEL COMPOSITIONS FROM THE CLASSS CONSISTING OF RESIDUAL PETROLEUM, COAL AND COKE WHICH COMPRISES BURNING SAID FUEL IN THE PRESENCE OF A MINOR AMOUNT, RELATIVE TO SAID FUEL, OF AN ADDITIVE CONSISTING ESSENTIALLY OF A FIRST CONSTITUENT WHICH COMPRISES A MEMBER OF THE FIRST CLASS CONSISTING OF ALUMINUM, MAGNESIUM AND MANGANESE, A SECOND CONSTITUENT WHICH COMPRISES A MEMBER OF SAID FIRST CLASS OTHER THAN THAT COMPRISING SAID FIRST CONSTITUENT, AND A THIRD CONSTITUENT WHICH COMPRISES IRON, SAID FIRST CONSTITUENT BEING PRESENT IN ACTIVE ELEMENT PROPORTIONS BY WEIGHT BETWEEN 5 AND 30 PARTS, SAID SECOND AND THIRD CONSTITUENTS BEING PRESENT IN ACTIVE ELEMENT PROPORTIONS BY WEIGHT BETWEEN 0.35 AND 10 PARTS. 